Production of nu-dihydro-anthraquinoneazines



Patented Mar. 1, 1932 UNITED STATES JAMES OGILVIE, 0F BUFFALO, NEW YORK, ASSIGNOR TO NATIONAL ANILINE & CHEMI- PATENT OFFICE.

CAL COMPANY, INC., OF NEW YORK, N. Y., A CORPORATION OF NEW YORK No Drawing.

Other objects of the invention. will in part be obvious and will in after. 7 Y

The invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others thereof, which will be exemplifiedin part appear hereinthe process hereinafter disclosed, and the scope of the invention will be indicated in the claims; i

The conversion of 1.2.2.1-anthraquinoneazines to the corresponding N-dihydroazines has previously been accomplished by reduction with alkaline sodium hydrosulfite to the leuco form and oxidation of the resulting leuco compound with air to the N-dihydroazine. A milder reduction of the 1.2.2.1 anthraqninoneazines produces intermediate compounds known as anthraquinoneazhydrines, and a stronger reduction of the 1.2.21-anthraquinoneazines, such as distillation with zinc dust, eventually eliminates the oxygen of the keto groups, producing anthracenazines as the final product. The anthraquinoneazine dyestuffs are usually marketed in the N-dihydroazine form.

In the practice of the present invention, 1.2.2.lanthraquin'oneazine, and derivatives thereof which contain substituents in the anthraquinonenucleus, such as chlorine, bromine, alkyl, sulfo, amino, hydroxy, etc., may be reduced to the N-dihydroazineform by subjecting them to the reducing action of a polyvalent metal in the presence of a mineral or inorganic acid excepting nitric acid.

PRODUCTION OF N-DII-IYDRO-ANTHRAQUIN'ONEAZINES Application filed August 6, 1929. Serial 1T0. 383,971.

anthraquinone nucleus, by the action ofa metal in the presence of the inorganic acid in the manner of the present nvention, the conversion to the Nd1hydroaz1ne 1s accomplished without theelimination of substitu cuts in the anthraquinone nucleus. Further,

when a halogenated anthraquinoneazine hasbeen produced by the halogenation of the anthraquinoneazine in the presence of an acid,

e. g., sulfuric acid, the reduction is carried out preferably by treatin'gthe crudevhalogenation mass with the finely divided metal. As illustrative embodiments of a manner in which the invention may be carried out in practice, the following examples are presented. The parts are by weight.

Example 1.-350 parts indanthrene, containing about 93.4% of N-dihydro-anthraquinoneazine (.74 mols) are chlorinatedat 34'35 (l, in 4550 parts of 94.5% sulfuric acid, by the introduction of 90' parts of chlorine gas (2.8 mols); The gas is introduced as :fast as it is absorbed. The chlorination reaction mass which containschlorinated -N- dihydro-anthraquinoneazine, and also somechlorinated anthraquinoneazine, is then cooled to about 20 C. and 8 parts of aluminum bronze (i. e., pulverized aluminum) are now added in small portions at a time, permitting the reaction to subside before adding each subsequent portion. During the reduction the temperature is permitted to rise to 28 29 C. at which point it is maintained for about three hours after the last of the aluminum has been added, or until reduction is completed. The completion .of the reduction may be detected by removinga sample of the reaction mass and placing it in water. A blue violet precipitate indicates the completion of the reduction. Whenreduction is finished, the mass is added to 2150 parts of water which has been preheated to (1, and is then further diluted with cold water, filtered and washed.

In this chlorination, there is produced a mixture containing probably the azine, theis accompanied by considerable evolution of heat. It is therefore desirable to control .the temperature of the reduction in order to prevent mechanical loss of product due, for example, ,to foaming over, and to prevent a too vigorous reduction. When utilizing concentrated sulfuic acid, it is preferred to employ temperatures of about 35 (1., although higher temperatures may be employed. With dilute sulfuric :acids higher temperatures may be attained without obtaining too vigorous reduction.

The excess of aluminum over that required for the reduction dissolves-only slowly in the surfuric acid. The presence of the 'GXC'BSS of aluminum bronze in the dyestutf, especially where the dyestuii' is to be made into a printing paste, is highly objectionable. Therefore, the reduction mass is drowned inwater to produce a dilute solution of sulfuric acid which dissolves the excess of aluminum more readily. Preferably, the water used to dilute thereduction-mass is preheated, for the speed of reaction between the aluminum and the su'lfuricacid isaccelerated by heating; Also, instead of using concentrated sulfuric acid, the reduction may be carried out by first diluting the chlorination mass then adding the.

metal with or without the aid of external heating. The reduction may also be accom plished in acids in which the indanthrene compounds are-not soluble such as, for example, dilute sulfuric acid, or in hydrochloric acid.

I Ewample .2('60 parts of dibrom-anthraquinoneazine arevdissolved in 600 parts of 93.1

per cent sulfuric acid at about 20 C., and 6.4

parts of copper dustare added in small successive portions as described in Exa ple l, the temperature being permitted to rise to about '29'30 (lduring the reaction. The

reduction mass is agitated at 2930? C. until the reduction is complete, and is then drowned in 300 parts of water preheated to about 6., and then diluted with cold water, filtered and washed. 7

' Example 3.15 parts of trichloranthraquinoneazine are dissolved in 150 parts 66 Be. sulfuric acid at about-20 (1., and a-O.5 part .of aluminum dust is added in small successive 35 portions as described above, the temperature being permitted to rise to about 2930 C. during the reaction. The reduction mass is agitated at 2930 (1, until reduction is complete, and is then drowned in parts of water, diluted with cold water, filtered and washed.

In a corresponding way, 1.2.2.1-anthraquinonea-Zine, or derivatives thereof which contain other substituents in the anthraq'uinone nucleus such as alkyl, sulfo, amino, hydroxy, .etc. maybe reduced.

It will be understood of course that the invention in its breaderaspect is not limited to the specific materials and amounts thereof set forth in the preceding examples. Other polyvalent metals, preferably those having .an atomic number lying between 13 and 30 inclusive and which form soluble sulfates, such as, among others, zinc or iron may be used in the place of the aluminum or copper above specified. Whereas the quantity of aluminum has preferably been given above as %I'ClS of a gram atom per gram molecule of anthraquinoneazine it is to be noted that in the use of a bivalent metal, for example, copper, an :equal .inolecular proportion of metal and anthraquinoneazine or azhydrine is employed it being particularlydesirable when using abivalent metal to have an excess present. Furthermore, it is preferred in general to utilize the -metals in finely divided form. However, desired, coarser or granulated particles maybe used.'

The sulfuric acid used in the reduction may be replaced by other mineral acids. Hydrochloricacid'is suitable for use at low temperatures; but, since it has :a .tendency to chlorinate the nonhalogenated indanthreneazines or the mono halogenated vindanthreneazines, this acid is not suitable for the reduction at highv temperatures of .anthraquinoneazines .containingless than two atoms of halogen, unless it is desired to produce .a chlorinated N dil1yd-ro-anthraquinoneazine.

The reduced .dyestufi's obtained in the practiceof the present invention. are generally of an amorphous appearance when viewed under the microscope and are especially advanta'gcous in the dyeing of textiles by the pad and jig method.

Since certain changes may be made in carrying out the above process without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in .a limiting sense.

Having described my invention, what I claim :as new and desire to secure by Letters Patent is: i

1. Aiprocess for the production of N -di-.

between 13 and 30, inclusive, and which forms a soluble sulfate.

2. A process for the production of N-dihydro-anthraquinoneazines, which comprises subjecting an 1.2.2.1-anthraquinoneazine in concentrated sulfuric acid to the reducing action of a polyvalent metal having an atomic number lying between 13 and 30 inclusive and which forms a soluble sulfate.

3. A process for the production of an N- dihydro-anthraquinoneazine, which comprises subjecting an 1.2.2.1-anthraquinoneazine to the reducing action of aluminum and sulfuric acid.

4. A process for the production of an N-dihydro-anthraquinoneazine, which comprises subjecting an 12.2.l'-anthraquinoneazine containing halogen as a substituent in the anthraquinone nucleus, to the reducing action of aluminum in the presence of sulfuric acid.

5. A process for the production of an N-dihydro-anthraquinoneazine, which comprises halogenating an 1.2.2.1-anthraquinoneazine in the presence of sulfuric acid and adding aluminum to the halogenation reaction mass to reduce the halogenated anthraquinonazine to the N-dihydro form.

6. A process for the production of an N-dihydro-anthraquinoneazine, which comprises introducing chlorine into a sulfuric acid solution of an 1.2.2.l-anthraquinoneazine, and after chlorination adding aluminum to the reaction mass to reduce the chlorinated anthraquinoneazine to the N-dihydro form.

7. A process for the production of N-dihydro-anthraquinoneazines, which comprises subjecting an 1.2.2.1-anthraquinoneazine in the presence of a mineral acid excepting nitric acid, to the reducing action of a polyvalent metal having an atomic number lying between 13 and .30 inclusive and which forms a soluble sulfate.

8. A process for the production of N-dihydro-anthraquinoneazines, which comprises subjecting an 1.2.2.1-anthraquinoneazine in the presence of sulfuric acid, to the reducing action of a polyvalent metal having an atomic number lying between 13 and 30 in elusive and which forms a soluble sulfate.

9. A process for the production of N-dihydro-anthraquinoneazines, which comprises subjecting an- 1.2.9..1-anthraquinoneazine containing halogen as a substituent in the anthraquinone nucleus, in the presence of a mineral acid excepting nitric acid to the reducing action of a polyvalent metal having an atomic number lying between 13 and 30 inclusive and which forms a soluble sulfate.

10. A process for the production of N-dihydro-anthraquinoneazines, which comprises subjecting an 1.2.2.1'-anthraquinoneazine containing halogen as a substituent in the anthraquinone nucleus, in the presence of sulfuric acid to the reducing action of a poly- .valent metal having an atomic number lying between 1.3 and 30 inclusive. and which forms a soluble sulfate.

11. A process for the production of N-diatomic number lying between 13 and 30 ina elusive andwhich forms a soluble sulfate, in the presence of a mineral acid excepting nitric acid. i

12. A process for the production of N-dihydro-anthraquinoncazines, which comprises subjecting an 1.2.21-anthraquinoneazine containing chlorme as a substltuent 1n, the

-anthraquin'one nucleus, to the reducing action of a polyvalent metal having an atomic number lying between '13 and 30 inclusive and which forms a soluble sulfate, in the presence of sulfuric'acid.

13. A process for the production of N-dihydro-anthraquinoneazines, which comprises subjecting an 12.2.1-anthraquinoneazine.

containing not more than two substituent halogenatoms in the anthraquinone. nucleus,

to the reducing actionof a polyvalent metal having. an atomic number lying between 13 and 30 inclusive and which forms a soluble sulfate, in the presence of a mineral acidexcepting nitric acid.

. hydro.-anthraquinoneazines,.which comprises subjecting an 12.2.1-anthraquinoneazine containing not more than two substltuent halogen atoms in the anthraquinone nucleus, to, the reducing action of a polyvalent metal having an atomic number lying between 13 and 30 inclusive and which forms a soluble-:;-

sulfate, in the presence of sulfuric acid.

15. A process for the production of N-dihydro-anthraquinoneazines, which comprises subjecting an 1.2.2.1-anthraquinoneazine containing not more than two substituent' chlorine atoms in the anthraquinone nucleus, to the reducing action of a polyvalent metal having an atomic number lying between 13 and 30 inclusive and which forms a soluble sulfate, in the presence of a mineral acid excepting nitric acid.

16. A process for the production of N-dihydro-anthraquinoneazines, which comprises subjecting an 1.22.1-anthraquinoneazine containing not more than two substituent elusive and which forms a -'solable', su liate,

to reduce-the halogenated anthraquinoneazine to the N-dihydro form.

18. A process'fol' the prod-notion of N-di- 5 hydro-'anthraquinoneazines, Which comprises ha logenating an 1.2.2.I-anthraquinoneazine in the presence of sulztui'i'c acid and adding :to the halogenation reaction mass a polyvalent metal having an atomic number lying j between 1-3and30 inclusive and which forms :a soluble sulfate, to reduce the halogenated 'iwnthraqninoneazine to the N-dihyd ro form.

19. A process for theproduction of an N-d i- A hydro antlrraquinoneazine, which comprises -1 chlorinating :a-n 1.22.1-anthraqninoneazine in the presence of a mineral acid excepting nitric acid and adding to the chlorination :reaction mass a polyValen-t metal having an M atomic number lying between 13 and -30 in- '1 elusive and which forms a soluble sulfate.

20. Aprocess'for the productionof an N-d ihydro-anthraquinoneazin'e, which comprises chlorinating an 1.22.l-a ntlrraqninoneazine inth'e presence of sulfuric acid and adding to the chlorination reaction mass a polywail'enft metal having an atomic number lying between 1-3 and 39 inclusive and which forms a soluble sulfate. 21. A process for the production of N-di hydroanthraquinoneazines which comprises subjecting :a-n 122CI-anthraquinoneazine containing halogen as a substi'tuent inthe :ant'hraquinone nucleus in concentrated sul furic acid to the reducing action of alumiznum.

1n w'itnesswhereof, I have hereunto set any ham-d.

JAMES 'OGILWE. 

